2005 Fiscal Year Final Research Report Summary
Precise Solid-State NME Analyses of Noncrystalline Organized Structure and Dynamics of Polymeric Functional Materials
| Project/Area Number |
16350125
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Polymer/Textile materials
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| Research Institution | KYOTO UNIVERSITY |
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Principal Investigator |
HORII Fumitaka KYOTO UNIVERSITY, Institute for Chemical Research, Professor, 化学研究所, 教授 (70124758)
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| Co-Investigator(Kenkyū-buntansha) |
KAJI Hironori KYOTO UNIVERSITY, Institute for Chemical Research, Associate Professor, 化学研究所, 助教授 (30263148)
HIRAI Asako KYOTO UNIVERSITY, Institute for Chemical Research, Assistant Professor, 化学研究所, 助手 (20156623)
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| Project Period (FY) |
2004 – 2005
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| Keywords | Noncrystalline structure / Solid-state NMR / Dynamics / Local structure / Precise structure analyses / Resonance-line assignments / Iodine complexes / Bacterial cellulose |
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| Research Abstract |
To characterize the detailed structure of noncrystalline organic materials such as organic solar cells and organic EL devises, two-dimensional double quantum solid-state NMR spectroscopy(2D DOQSY) has been developed because diffractometry is not effective in those noncrystalline materials. This method was applied to the detailed characterization of 10% CO ^<13>C-enriched poly(ethylene terephthalate)(PET) that was quenched from the melt to iced water. About 45% isotropic component was found to be contained in the intermolecular distance of about 0.5nm for the neighboring CO groups. As for the anisotropic component in PET, Eulerian angles ψ and φ are specifically widely distributed : ψ is distributed around 0 degree pseudo-exponentially while φ around about 35 degrees in a Gaussian distribution way. On the basis of these results, the structure and dynamics of charge-carrier materials for the EL devices were characterized in detail by ^<13>C,^<15>N,^2H NMR and quantum chemistry calculations.
To develop a new assignment method of NMR resonance lines for solid materials including noncrystalline materials, homo-nuclear cross polarization (HNCP) was evaluated in detail and ^<13>C-^<13>C J-coupling was found to be available for that purpose under relatively high-speed magic-angle spinning. We also successfully characterized the structure and dynamics of poly(vinyl alcohol)-iodine complexes, which are used for polarizing films for liquid crystal displays, by solid-state ^<13>C NMR and proposed a new structure model called "Hexagonal Aggregation Model." Moreover, the basic molecular assembly, sub-elementary fibrils (SEFs), after biosynthesis for bacterial cellulose, was characterized in detail by solid-state ^<13>C NMR for the never-dried specimens for the first time and structure models were proposed for the formation mechanism of the hierarchical structure in this system including crystallization associated with crystal nucleation and growth.
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